TWI757325B - 用於產生薄無機膜的方法 - Google Patents
用於產生薄無機膜的方法 Download PDFInfo
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- TWI757325B TWI757325B TW106129345A TW106129345A TWI757325B TW I757325 B TWI757325 B TW I757325B TW 106129345 A TW106129345 A TW 106129345A TW 106129345 A TW106129345 A TW 106129345A TW I757325 B TWI757325 B TW I757325B
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- Taiwan
- Prior art keywords
- compound
- general formula
- alkenyl
- group
- alkyl
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 87
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 239000003446 ligand Substances 0.000 claims abstract description 41
- 239000007787 solid Substances 0.000 claims abstract description 39
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 28
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 238000000231 atomic layer deposition Methods 0.000 abstract description 9
- -1 n-octyl Chemical group 0.000 description 53
- 239000010408 film Substances 0.000 description 38
- 239000010410 layer Substances 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000000443 aerosol Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 210000002381 plasma Anatomy 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 229910000071 diazene Inorganic materials 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 4
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- JAIWFUHVFMKUFA-UHFFFAOYSA-N N-propan-2-yl-1-(1H-pyrrol-2-yl)methanimine Chemical compound C(C)(C)N=CC=1NC=CC=1 JAIWFUHVFMKUFA-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- SNACPYDCTQVUSO-UHFFFAOYSA-N C(C)(C)(C)N=CC=1NC=CC=1 Chemical compound C(C)(C)(C)N=CC=1NC=CC=1 SNACPYDCTQVUSO-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000003877 atomic layer epitaxy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000572 ellipsometry Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 125000004587 thienothienyl group Chemical group S1C(=CC2=C1C=CS2)* 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000002424 x-ray crystallography Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- POIVWEXWFKSJHL-UHFFFAOYSA-N 2-(dimethylamino)propan-2-ol Chemical compound CN(C)C(C)(C)O POIVWEXWFKSJHL-UHFFFAOYSA-N 0.000 description 1
- GVHIREZHTRULPT-UHFFFAOYSA-N 2-methyl-n-trimethylsilylpropan-2-amine Chemical compound CC(C)(C)N[Si](C)(C)C GVHIREZHTRULPT-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- RYFJKGWMVVZSLH-UHFFFAOYSA-N 4-propan-2-yliminopentan-2-one Chemical compound CC(C)N=C(C)CC(C)=O RYFJKGWMVVZSLH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical group CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910018999 CoSi2 Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XIEFLMRAESTBGY-UHFFFAOYSA-N N-ethyl-1-(1H-pyrrol-2-yl)methanimine Chemical compound C(C)N=CC=1NC=CC=1 XIEFLMRAESTBGY-UHFFFAOYSA-N 0.000 description 1
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- 125000005493 quinolyl group Chemical group 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000010896 thin film analysis Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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Abstract
Description
本發明屬於在基板上產生薄無機膜之方法之領域,特定言之原子層沉積法之領域。
隨著例如在半導體工業中正在進行的小型化發展,對基板上之薄無機膜之需要增加,同時對此類膜之品質的要求變得更加嚴格。薄無機膜服務於不同目的,諸如精密結構之障壁層、介電質、傳導特徵、罩蓋或分隔。已知若干用於產生薄無機膜之方法。其中之一為將氣態成膜化合物沉積在基板上。為使金屬原子在中等溫度下變為氣態,有必要例如藉由使金屬與適合之配位體錯合以提供揮發性前驅物。此等配位體需要在錯合金屬沉積至基板上之後移除。
Choi等人在Chemistry of Materials,第15卷(2003),第20號,第3735至3738頁中揭示在化學氣相沉積中Ni[P(OMe)3]4之用途。然而,特定言之對於原子層沉積需要較高反應性及同時高穩定性。
本發明之一個目標為提供一種用於在經濟上可實行之條件下在固體基板上產生具有高品質及高再現性的含有Mn、Ni及/或Co之膜的方法。合乎需要的是此方法可在包含Mn、Ni或Co之前驅物與固體基板接
觸之前在該前驅物之分解儘可能少的情況下進行。同時,需要提供前驅物在沉積於固體基板上之後易於分解之方法。本發明亦旨在提供使用含有Mn、Ni或Co之前驅物的方法,該等前驅物可易於經修飾且仍保持穩定以便使前驅物之特性適合於特定需求。
此等目標藉由用於產生無機膜之方法來達成,該方法包含使通式(I)化合物沉積至固體基板上
其中M為Mn、Ni或Co,X為與M配位之配位體,n為0、1、2、3或4;R1為烷基、烯基、芳基、鹵素或矽烷基,R2為烷基、烯基、芳基或矽烷基,p及q為1或2,其中p+q=3,及m為1、2或3。
本發明進一步關於通式(I)化合物之用途,其中M為Mn、Ni或Co,X為與M配位之配位體,n為0、1、2、3或4;R1為烷基、烯基、芳基、鹵素或矽烷基,R2為烷基、烯基、芳基或矽烷基,p及q為1或2,其中p+q=3,及m為1、2或3
其用於在固體基板上之膜形成方法。
本發明進一步關於通式(I)化合物,其中M為Mn、Ni或Co,X為與M配位之配位體,其中至少一個X經由氮原子與M配位,n為0、1、2、3或4;R1為烷基、烯基、芳基、鹵素或矽烷基,R2為烷基、烯基、芳基或矽烷基,p及q為1或2,其中p+q=3,及m為1、2或3。
本發明之較佳具體實例可見於實施方式及申請專利範圍中。不同具體實例之組合屬於本發明範疇內。
在通式(I)化合物中,R1為烷基、烯基、芳基、鹵素或矽烷基,較佳為烷基或矽烷基,尤其烷基。R2為烷基、烯基、芳基或矽烷基,較佳為烷基或矽烷基,尤其烷基。R1及R2可彼此相同或不同。在存在兩個R1之情況下,亦即若p為2,則兩個R1可彼此相同或不同。在存在兩個R2之情況下,亦即若q為2,則兩個R2可彼此相同或不同。有可能兩個R1或兩個R2或一個R1及一個R2彼此連接以使得其形成包括其所連接之磷原子的環。有可能若至少一個R1及R2為烯基或芳基,則此環含有一個或多個雙鍵。指數m可為1、2或3,較佳為1或2。若m大於1,亦即式(I)化合物中 存在超過一個膦配位體,則在不同膦配位體中相對應的R1及R2可彼此相同或不同,較佳地其為相同的。
烷基可為直鏈或分支鏈。直鏈烷基之實例為甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基。分支鏈烷基之實例為異丙基、異丁基、第二丁基、第三丁基、2-甲基-戊基、2-乙基-己基、環丙基、環己基、二氫茚基、降冰片基。較佳地,烷基為C1至C8烷基,更佳地為C1至C6烷基,尤其C1至C4烷基,諸如甲基、乙基、異丙基或第三丁基。烷基可例如經鹵素(諸如F、Cl、Br、I,尤其F);經羥基;經醚基;或經胺(諸如二烷基胺)取代。
烯基含有至少一個碳-碳雙鍵。雙鍵可包括烯基鍵結至分子之其餘部分所用的碳原子,或雙鍵可位於較遠離烯基鍵結至分子之其餘部分的位置,較佳地雙鍵位於較遠離烯基鍵結至分子之其餘部分的位置。烯基可為直鏈或分支鏈。直鏈烯基(其中雙鍵包括烯基鍵結至分子之其餘部分所用的碳原子)之實例包括1-乙烯基、1-丙烯基、1-正丁烯基、1-正戊烯基、1-正己烯基、1-正庚烯基、1-正辛烯基。直鏈烯基(其中雙鍵位於較遠離烯基鍵結至分子之其餘部分的位置)之實例包括1-正丙烯-3-基、2-丁烯-1-基、1-丁烯-3-基、1-丁烯-4-基、1-己烯-6-基。分支鏈烯基(其中雙鍵包括烯基鍵結至分子之其餘部分所用的碳原子)之實例包括1-丙烯-2-基、1-正丁烯-2-基、2-丁烯-2-基、環戊烯-1-基、環己烯-1-基。分支鏈烯基(其中雙鍵位於較遠離烯基鍵結至分子之其餘部分的位置)之實例包括2-甲基-1-丁烯-4-基、環戊烯-3-基、環己烯-3-基。具有超過一個雙鍵之烯基的實例包括1,3-丁二烯-1-基、1,3-丁二烯-2-基、環戊二烯-5-基。
芳基包括芳族烴,諸如苯基、萘基、蒽基、菲基;及雜芳族基團,諸如吡咯基、呋喃基、噻吩基、吡啶基、喹啉基、苯并呋喃基、苯并噻吩基(benzothiophenyl)、噻吩并噻吩基(thienothienyl)。若干此等基團或此等基團之組合亦為可能的,如聯二苯、噻吩并苯基或呋喃基噻吩基。芳基可例如經鹵素(如氟、氯、溴、碘);經假鹵素(如氰根、氰酸根、硫氰酸根);經醇;經烷基鏈或烷氧基鏈取代。較佳為芳族烴,更佳為苯基。
鹵素包括氟、氯、溴及碘,較佳包括氟或氯,尤其氟。
矽烷基為典型地具有三個取代基之矽原子。較佳地,矽烷基具有式SiE3,其中E彼此獨立地為氫、烷基、烯基、芳基或矽烷基。有可能所有三個E相同,或兩個E相同且另一個E不同,或所有三個E彼此不同。亦有可能兩個E一起形成包括Si原子之環。烷基及芳基如上文所描述。矽烷基之實例包括SiH3、甲基矽烷基、三甲基矽烷基、三乙基矽烷基、三正丙基矽烷基、三異丙基矽烷基、三環己基矽烷基、二甲基-第三丁基矽烷基、二甲基環己基矽烷基、甲基-二異丙基矽烷基、三苯基矽烷基、苯基矽烷基、二甲基苯基矽烷基、五甲基二矽烷基。
烷氧基為經由氧原子連接至剩餘分子之烷基。芳氧基為經由氧原子連接至剩餘分子之芳基。
根據本發明,通式(I)化合物中之配位體X可為與M配位之任何配位體。指數n可為0、1、2、3或4,較佳為2或3,尤其2。n與m之總和,亦即金屬M帶有的配位體之數目,視該金屬及其氧化態而定。Mn可帶有至多5個配位體,亦即n+m5,而Ni及Co典型地帶有至多4個配位體,亦即n+m4。若n為2、3或4,亦即通式(I)化合物含有兩 個、三個或四個X,則其可彼此相同或不同,較佳地其為相同的。任何或所有X可在M之任何配位體層中,例如在內部配位體層中、在外部配位體層中或僅與M鬆散結合。較佳地,X在M之內部配位體層中。咸信,若所有配位體X均在M之內部配位體層中,則通式(I)化合物之揮發性較高以使得其可在不分解的情況下變為氣態或氣溶膠狀態。
根據本發明通式(I)化合物中之配位體X包括鹵素陰離子(如氟離子、氯離子、溴離子或碘離子)及假鹵素陰離子(如氰根、異氰根、氰酸根、異氰酸根、硫氰酸根、異硫氰酸根或疊氮根)。其他適合之配位體X為烷基陰離子,如甲基、乙基、丁基或新戊基陰離子;以及帶有烷基之矽,諸如三甲基矽烷基甲基。其他可能之配位體X為氫負離子、一氧化氮(nitric oxide;NO)及一氧化碳(carbonmonoxide;CO)。
此外,X可為經由中性或陰離子型氮原子與M配位之配位體,例如藉由在與M配位之前脫質子化。此類配位體包括胺配位體,其中配位氮原子為脂族,如在二烷基胺、哌啶、吡咯啶、嗎啉、烷基矽烷胺(諸如六甲基二矽氮烷或三甲基矽烷基第三丁基胺)中;或芳族,如在吡咯、吲哚、吡啶或吡嗪中。較佳地,X為經由至少兩種中性或陰離子型氮原子配位之配位體。此等配位體包括脒基,諸如乙脒或N,N'-雙-異丙基乙脒;胍基,諸如胍;胺基亞胺,諸如2-N-第三丁基胺基-2-甲基丙醛-N-第三丁基亞胺;二亞胺,諸如乙二醛-N,N'-雙-異丙基-二亞胺、乙二醛-N,N'-雙-第三丁基-二亞胺或2,4-戊二酮-二亞胺;二酮亞胺,諸如N,N'-2,4-戊二酮亞胺;亞胺基吡咯,包括吡咯-2-甲醛-烷基亞胺,諸如吡咯-2-甲醛-乙基亞胺、吡咯-2-甲醛-異丙基亞胺或吡咯-2-甲醛-第三丁基亞胺以及吡咯-2,5-雙甲醛-烷基二 亞胺,諸如吡咯-2,5-雙甲醛-第三丁基二亞胺。
亦有可能X為其中氧原子配位至M之配位體。實例為烷醇根、四氫呋喃、乙醯基丙酮酸根或1,1,1,5,5,5-五氟乙醯基丙酮。其他適合於X之實例包括均配位至M之氮原子及氧原子,包括二甲胺基異丙醇、甲醯胺、乙醯胺、2,4-戊二酮-N-烷基亞胺(諸如2,4-戊二酮-N-異丙基亞胺)。
X亦可為用π鍵與M配位之不飽和烴。此等烴可為脂族或芳族。不飽和烴包括烯烴,如乙烯、丙烯、異丁烯、環己烯、環辛烯、環辛二烯、苯乙烯;及炔烴,如乙炔、丙炔、2-丁炔。X亦可為可經由陰離子及不飽和鍵配位之不飽和陰離子型烴,諸如烯丙基、2-甲基-烯丙基或1,3-雙(三甲基矽烷基)-烯丙基。經由π鍵配位至M之芳族X包括環戊二烯陰離子及其衍生物;苯及其衍生物(諸如甲苯或二甲苯)。
較佳地,配位體X為經由氮與M配位之配位體,或X為脂族烴、烷醇根、氰根、溴離子、CO或NO。尤其較佳之配位體X為甲基、乙基、丙基、新戊基、三甲基矽烷基甲基、烯丙基、2-甲基-烯丙基、1,3-雙(三甲基矽烷基)-烯丙基、2-N-第三丁基胺基-2-甲基丙醛-N-第三丁基亞胺、N,N'-雙-異丙基乙眯、乙二醛-N,N'-雙-第三丁基-二亞胺、乙二醛-N,N'-雙-異丙基-二亞胺、吡咯-2-甲醛-異丙基亞胺或吡咯-2-甲醛-第三丁基亞胺、甲醇根、乙醇根、CO、NO、氰根、溴離子、乙烯、環辛烯、環辛二烯、或2-丁炔,尤其2-甲基-烯丙基、N,N'-雙-異丙基乙眯、乙二醛-N,N'-雙-第三丁基-二亞胺、吡咯-2-甲醛-異丙基亞胺、CO及NO。
若通式(I)化合物中存在超過一個配位體X,則較佳地至少一個X為如上文所描述之較佳配位體,例如較佳地至少一個X經由氮原 子與M配位或X為脂族烴、烷醇根、氰根、溴離子、CO或NO,更佳地至少一個X經由氮原子與M配位。
金屬M為Mn、Ni或Co,亦即錳、鎳或鈷,較佳為Ni或Co,尤其Co。金屬M可呈不同的氧化態,例如0、+1、+2、+3或+4。較佳地,X、n及m經選擇以使得通式(I)化合物為電中性。
較佳的是,通式(I)化合物之分子量為至多1000g/mol,更佳為至多800g/mol,尤其至多600g/mol。
通式(I)化合物之一些較佳之實例在下表中給出。
Me表示甲基,Et表示乙基,i-Pr表示異丙基,HMDS表示六甲基二矽烷胺化物,Cp表示環戊二烯基,TBGI表示N,N'-二-第三丁基乙二醛二亞胺,nP表示新戊基。
用於根據本發明之方法中的通式(I)化合物較佳地以高純度使用以達成最佳結果。高純度意謂所採用物質含有至少90wt%通式(I)化合物,較佳至少95wt%通式(I)化合物,更佳至少98wt%通式(I)化合物,尤其至少99wt%通式(I)化合物。純度可藉由根據DIN 51721(Prufung fester Brennstoffe-Bestimmung des Gehaltes an Kohlenstoff und Wasserstoff-Verfahren nach Radmacher-Hoverath,2001年8月)之元素分析來測定。
通式(I)化合物可自氣態或氣溶膠狀態沉積。可藉由將其 加熱至高溫以使其變為氣態或氣溶膠狀態。在任何情況下均必須選擇低於通式(I)化合物之分解溫度的溫度。較佳地,加熱溫度在略高於室溫至300℃,更佳30℃至250℃,甚至更佳40℃至200℃,尤其50℃至150℃之範圍內。
另一使通式(I)化合物變為氣態或氣溶膠狀態之方法為如例如在US 2009/0 226 612 A1中所描述之直接液體注入(direct liquid injection;DLI)。在此方法中,通式(I)化合物典型地溶解於溶劑中且噴灑在載氣或真空中。視通式(I)化合物之蒸氣壓力、溫度及壓力而定,使通式(I)化合物變為氣態或變為氣溶膠狀態。可使用各種溶劑,其條件為通式(I)化合物在彼溶劑中展示足夠的溶解度,諸如至少1g/l,較佳至少10g/l,更佳至少100g/l。此等溶劑之實例為配位溶劑,諸如四氫呋喃、二烷、二乙氧基乙烷、吡啶;或非配位溶劑,諸如己烷、庚烷、苯、甲苯或二甲苯。溶劑混合物亦為適合的。包含通式(I)化合物之霧劑應含有極精細液滴或固體粒子。較佳地,液滴或固體粒子具有不超過500nm,更佳不超過100nm之重量平均直徑。液滴或固體粒子之重量平均直徑可藉由如ISO 22412:2008中所描述之動態光散射來測定。亦有可能通式(I)化合物之一部分呈氣態且其餘部分呈氣溶膠狀態,例如由於通式(I)化合物之有限的蒸氣壓,導致呈氣溶膠狀態之通式(I)化合物部分蒸發。
或者,可藉由如例如由J.Yang等人(Journal of Materials Chemistry C,第3卷(2015)第12098-12106頁)所描述之直接液體蒸發(direct liquid evaporation;DLE)使含金屬化合物變為氣態。在此方法中,使含金屬化合物或還原劑與溶劑(例如烴,諸如十四烷)混合,且在低於溶劑之沸 點下加熱。藉由蒸發溶劑,使含金屬化合物或還原劑變為氣態。此方法具有沒有粒子污染物形成於表面上的優勢。
較佳在減壓下使通式(I)化合物變為氣態或氣溶膠狀態。以此方式,該方法可通常在較低加熱溫度下進行,導致通式(I)化合物分解減少。
亦有可能使用加壓以將呈氣態或氣溶膠狀態之通式(I)化合物推向固體基板。通常,出於此目的,惰性氣體(諸如氮氣或氬氣)用作載氣。較佳地,壓力為10巴至10-7毫巴,更佳1巴至10-3毫巴,尤其10至0.1毫巴,諸如1毫巴。
亦有可能自溶液沉積通式(I)化合物或使通式(I)化合物與固體基板接觸。對於不足夠穩定以供蒸發之化合物而言自溶液沉積為有利的。然而,溶液需要具有高純度以避免在表面上之非所需的污染。自溶液沉積通常需要不會與通式(I)化合物反應之溶劑。溶劑之實例為醚(如乙醚、甲基-第三丁基醚、四氫呋喃、二烷);酮(如丙酮、甲基乙基酮、環戊酮);酯(如乙酸乙酯);內酯(如4-丁內酯);有機碳酸酯(如碳酸二乙酯、碳酸伸乙酯、碳酸伸乙烯酯);芳香烴(如苯、甲苯、二甲苯、均三甲苯、乙苯、苯乙烯);脂族烴(如正己烷、環己烷、異十一烷、十氫化萘、十六烷)。較佳為醚,尤其四氫呋喃。通式(I)化合物之濃度尤其視反應性及所需反應時間而定。典型地,濃度為0.1mmol/l至10mol/l,較佳1mmol/l至1mol/l,尤其10至100mmol/l。用於溶液沉積之反應溫度典型地低於用於自氣相或霧相沉積之反應溫度,典型地為20至150℃,較佳50至120℃,尤其60至100℃。
若基板與通式(I)化合物接觸,則沉積發生。一般而言,沉積方法可以兩種不同方式進行:將基板加熱至高於或低於通式(I)化合物之分解溫度。若將基板加熱至高於通式(I)化合物之分解溫度,則通式(I)化合物在固體基板之表面上持續分解,只要更多呈氣態或氣溶膠狀態之通式(I)化合物達到固體基板之表面即可。此方法典型地稱為化學氣相沉積(chemical vapor deposition;CVD)。通常,當有機材料自金屬M解除吸附時,均質組成物(例如金屬氧化物或氮化物)之無機層形成於固體基板上。典型地,將固體基板加熱至300℃至1000℃範圍內、較佳350℃至600℃範圍內之溫度。
或者,基板低於通式(I)化合物之分解溫度。典型地,固體基板在等於或低於使通式(I)化合物變為氣態或氣溶膠狀態之位置之溫度的溫度下,通常在室溫下或僅略微高於室溫。較佳地,基板之溫度比使通式(I)化合物變為氣態或氣溶膠狀態之位置之溫度低至少30℃。較佳地,基板溫度為室溫至400℃,更佳100℃至300℃,諸如150℃至220℃。
通式(I)化合物至固體基板上之沉積為物理吸附或化學吸附過程。較佳地,通式(I)化合物經化學吸附在固體基板上。可藉由使具有具所討論之基板表面之石英晶體的石英微量天平暴露於呈氣態或氣溶膠狀態之通式(I)化合物中來判定通式(I)化合物是否化學吸附至固體基板。藉由石英晶體之本徵頻率來記錄質量增加。在抽空置放石英晶體之腔室之後,若發生化學吸附,則質量應不減少至最初質量,而有約一單層之殘餘通式(I)化合物殘留。在發生通式(I)化合物至固體基板之化學吸附的大多數情況下,M之X射線光電子光譜(X-ray photoelectron spectroscopy;XPS) 信號(ISO 13424 EN-Surface chemical analysis-X-ray photoelectron spectroscopy-Reporting of results of thin-film analysis;2013年10月)由於與基板之鍵形成而發生變化。
若在根據本發明之方法中之基板之溫度保持低於通式(I)化合物之分解溫度,則典型地,單層沉積在固體基板上。一旦通式(I)之分子沉積在固體基板上,在其上之進一步沉積的可能性通常變小。因此,通式(I)化合物在固體基板上之沉積較佳表示自我限制性方法步驟。自我限制性沉積方法步驟之典型層厚度為0.01nm至1nm,較佳0.02nm至0.5nm,更佳0.03nm至0.4nm,尤其0.05nm至0.2nm。層厚度典型地藉由如PAS 1022 DE(Referenzverfahren zur Bestimmung von optischen und dielektrischen Materialeigenschaften sowie der Schichtdicke d ü nner Schichten mittels Ellipsometrie;2004年2月)中所描述之橢圓偏振法量測。
通常需要積聚與剛剛描述之彼等層相比更厚的層。為了在根據本發明之方法中實現此需要,較佳藉由移除所有配位體來分解所沉積之通式(I)化合物,其後進一步沉積通式(I)化合物。此工序較佳進行至少兩次,更佳至少10次,尤其至少50次。通常,此工序進行不超過1000次。在本發明之上下文中,移除所有配位體意謂移除所沉積之通式(I)化合物中配位體之總重量的至少95wt%,較佳至少98wt%,尤其至少99wt%。分解可以各種方式實現。固體基板之溫度可提高至高於分解溫度。
此外,有可能使所沉積之通式(I)化合物暴露於以下各者中:電漿,如氧電漿或氫電漿;氧化劑,如氧氣、氧自由基、臭氧、一氧化二氮(N2O)、一氧化氮(NO)、二氧化氮(NO2)或過氧化氫;還原劑, 如氫氣、醇、肼(hydroazine)或羥胺;或溶劑,如水。較佳使用氧化劑、電漿或水以獲得金屬氧化物層。較佳暴露於水、氧電漿或臭氧中。尤其較佳暴露於水中。若需要元素金屬層,則較佳使用還原劑。較佳實例為氫氣、氫自由基、氫電漿、氨、氨自由基、氨電漿、肼、N,N-二甲基肼、矽烷、二矽烷、三矽烷、環五矽烷、環六矽烷、二甲基矽烷、二乙基矽烷或三矽烷基胺;更佳為氫氣、氫自由基、氫電漿、氨、氨自由基、氨電漿、肼、N,N-二甲基肼、矽烷;尤其氫氣。還原劑可直接使得所沉積之通式(I)化合物分解或其可在藉由不同試劑(例如水)使所沉積之通式(I)化合物分解之後應用。對於金屬氮化物之層,較佳使用氨或肼。典型地,觀測到所產生之膜的低分解時間及高純度。
包含自我限制性方法步驟及後續自我限制性反應之沉積方法通常稱為原子層沉積(atomic layer deposition;ALD)。等效表述為分子層沉積(molecular layer deposition;MLD)或原子層磊晶法(atomic layer epitaxy;ALE)。因此,根據本發明之方法較佳為ALD方法。ALD方法由George詳細描述(Chemical Reviews 110(2010),111-131)。
在根據本發明之方法中,通式(I)化合物沉積於固體基板上。固體基板可為任何固體材料。此等材料包括例如金屬、半金屬、氧化物、氮化物及聚合物。亦有可能基板為不同材料之混合物。金屬之實例為鉭、鎢、鈷、鎳、鉑、釕、鈀、錳、鋁、鋼、鋅及銅。半金屬之實例為矽、鍺及砷化鎵。氧化物之實例為二氧化矽、二氧化鈦、氧化鋯及氧化鋅。氮化物之實例為氮化矽、氮化鋁、氮化鈦、氮化鉭及氮化鎵。聚合物之實例為聚對苯二甲酸乙二酯(polyethylene terephthalate;PET)、聚乙烯萘二甲酸 (polyethylene naphthalene-dicarboxylic acid;PEN)及聚醯胺。
固體基板可具有任何形狀。此等形狀包括各種尺寸之薄片板、膜、纖維、粒子,及具有溝槽或其他凹痕之基板。固體基板可具有任何尺寸。若固體基板具有粒子形狀,則粒子之尺寸可在低於100nm至若干公分,較佳1μm至1mm範圍內。為避免粒子或纖維在通式(I)化合物沉積至其上時彼此黏著,較佳使其保持運動。此可例如藉由攪拌、藉由旋轉鼓輪或藉由流體化床技術來實現。
根據本發明之方法之特定優勢為通式(I)化合物極具通用性,因此方法參數可在廣泛範圍中變化。因此,根據本發明之方法包括CVD方法以及ALD方法兩者。
視根據本發明之方法中以ALD方法形式進行之工序的數目而定,產生具有各種厚度之膜。較佳地,使通式(I)化合物沉積至固體基板上及分解所沉積之通式(I)化合物的工序進行至少兩次。此工序可重複許多次,例如10至500次,諸如50或100次。通常,此工序重複頻率不會超過1000次。理想地,膜之厚度與所進行之工序數目成比例。然而,實務上,對於前30至50個工序觀測到一些比例偏差。假定固體基板之表面結構之不規則性導致此非比例性。
根據本發明之方法之一個工序可耗費數毫秒至若干分鐘,較佳0.1秒至1分鐘,尤其1至10秒。在低於通式(I)化合物之分解溫度的溫度下使固體基板暴露於通式(I)化合物中之時間愈長,則所形成之膜愈規則且缺陷愈少。
根據本發明之方法得到膜。膜可為所沉積之式(I)化合物 之僅一個單層、通式(I)化合物之若干經連續沉積及分解之層或若干不同層(其中膜中之至少一個層藉由使用通式(I)化合物來產生)。膜可含有缺陷,如孔洞。然而,此等缺陷通常構成由膜覆蓋之表面積的低於一半。膜較佳為無機膜。為產生無機膜,所有有機配位體必須自如上文所描述之膜移除。更佳地,膜為元素金屬膜。視如上文所描述之膜形成方法而定,膜之厚度可為0.1nm至1μm或大於1μm。較佳地,膜之厚度為0.5nm至50nm。膜較佳具有極均一膜厚度,其意謂在基板上之不同位置處的膜厚度變化極小,通常小於10%,較佳小於5%。此外,膜較佳為基板表面上之保形膜。測定膜厚度及均一性之適合的方法為XPS或橢圓偏振法。
藉由根據本發明之方法所獲得之膜可用於電子元件中。電子元件可具有各種尺寸之結構特徵,例如10nm至100μm,諸如100nm或1μm。形成用於電子元件之膜的方法尤其適用於極其精細的結構。因此,較佳為尺寸低於1μm之電子元件。電子元件之實例為場效電晶體(field-effect transistor;FET)、太陽能電池、發光二極體、感測器或電容器。在諸如發光二極體或感光器之光學裝置中,根據本發明之膜用以提高反射光之層的反射指數。感測器之實例為氧感測器,其中例如若製備了金屬氧化物膜,則該膜可充當氧導體。在出自金屬氧化物半導體之場效電晶體(field-effect transistors out of metal oxide semiconductor;MOS-FET)中,膜可充當介電層或充當擴散障壁。亦有可能自膜製造半導體層,其中元素鎳-矽沉積在固體基板上。
較佳之電子元件為電晶體。較佳地,膜充當電晶體中之擴散障壁、接觸件、襯墊或罩蓋層。錳或鈷之擴散障壁尤其適用於避免銅接觸件擴散至介電質中,所述擴散障壁通常以自形成式銅障壁形式應用。若電晶體由矽製成,則有可能在沉積鎳或鈷及加熱之後,一些矽擴散至鎳中以形成例如NiSi或CoSi2。
圖1描繪化合物C-1之熱重量資料。
將NaN(SiMe3)2(7.34g,40.0mmol)於THF(40mL,-36℃)中之經冷卻溶液逐滴添加至CoCl2(2.60g,20.0mmol)於THF(20mL,-36℃)中之經冷卻漿液中。觀測到藍色至綠色之顏色變化。在室溫下攪拌1h之後,在真空下移除所有揮發物。暗綠色固體用戊烷萃取(3×30mL)且過濾通過P3玻璃料。移除溶劑得到呈綠色晶體狀之C-0(7.01g,77.5%)。雙重昇華(40℃/l毫托)各20h得到分析純樣品。藉由在-36℃下緩慢蒸發於戊烷中之溶液以獲得用於X射線結晶學之晶體。
1H-NMR(300MHz,C6D6):δ(ppm)=162.6(br,4 H,CH2CH2O or CH2CH2O),97.0(br,4 H,CH2CH2O or CH2CH2O),-16.4(br,36 H,SiMe3):
元素分析:C16H44CoN2OSi4計算值:C,42.53;H,9.82;N,6.20。實驗值:C,42.05;H,10.58;N,6.20。
C-0在102℃下之蒸氣壓力為1毫巴。在昇華後,於氣化之位置處觀測到金屬殘餘物。熱重量(thermogravimetric;TG)分析揭示在300℃下殘餘質量為5.1%,DTA最大值為在159℃下。
將溶解於低溫Et2O(10mL,-36℃)中之P(OEt)iPr2(3.95g,24.4mmol)逐滴添加至[Co(N(SiMe3)2)2(THF)](C-0)(10.0g,22.1mmol)於Et2O(20mL,-36℃)中之經冷卻溶液中。將混合物在室溫下攪拌3天。於真空下移除溶劑得到呈粗產物形式之C-1。昇華(70℃/4毫托)16h得到呈綠色固體狀之分析純樣品(9.8g,82%產率)。藉由在-36℃下緩慢蒸發戊烷溶液以獲得用於X射線結晶學之晶體。
1H-NMR(300MHz,C6D6):δ(ppm)=55.8(br,6 H,P(CH(CH3)2),52.5(br,2 H,P(OCH2CH3),29.6(br,6 H,P(CH(CH3)2),9.5(br,3 H,P(OCH2CH3),-20.5(br,36 H,Si(CH3)3)。
元素分析:C20H55CoN2OPSi4計算值:C,44.3;H,10.2;N,5.2。實驗值:C,42.8;H,10.0;N4.9。
C-1在112℃下之蒸氣壓為1毫巴。在昇華後,於氣化之位置處未觀測到殘餘物。TG及DTA展示於圖1中。在300℃下殘餘質量為0.7%,DTA最大值為在142℃下。
Claims (15)
- 如申請專利範圍第1項之方法,其中R1及R2為烷基。
- 如申請專利範圍第1項或第2項之方法,其中R1及R2為甲基、乙基、異丙基或第三丁基。
- 如申請專利範圍第1項或第2項之方法,其中m為1。
- 如申請專利範圍第1項或第2項之方法,其中至少一個X為陰離子型配位體。
- 如申請專利範圍第1項或第2項之方法,其中M為Co。
- 如申請專利範圍第1項或第2項之方法,其中該通式(I)化合物經化學吸附在固體基板之表面上。
- 如申請專利範圍第1項或第2項之方法,其中所沉積之通式(I)化合物藉由移除所有配位體來分解。
- 如申請專利範圍第8項之方法,其中該所沉積之通式(I)化合物暴露於還原劑中。
- 如申請專利範圍第9項之方法,其中使該通式(I)之化合物沉積至固體基板上及分解該所沉積之通式(I)之化合物的工序進行至少兩次。
- 如申請專利範圍第12項之化合物,其中M為Co,m為1及n為2。
- 如申請專利範圍第12項或第13項之化合物,其中R1及R2為甲基、乙基、異丙基或第三丁基。
- 如申請專利範圍第12項或第13項之化合物,其中至少一個X為雙-(三甲基矽烷基)胺。
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